Manufacture of dyestuffs of the anthraquinone series



Patented Feb. 21, 1933 UNITED STATES PATENT SAMUEL VON ALLMEN, OF BASEL, SWITZERLAND, ASSIGNOR TO FIRM CHEMICAL WORKS FORMERLY SANDOZ, OF BASEL, SWITZERLAND MANUFACTURE OF DYESTUFFS OF THE ANTHRAQUINONE SERIES No Drawing. Application filed July 8, 1930, Serial No. 466,610, and in. Germany July 12, 1929.

My invention relates to a process for the manufacture of new dyestuffs of the anthraquinone series, which consists in condensing anthraquinone derivatives of the general formula:

wherein X represents an amino, substituted amino, hydroxy or alkoxy group, Y represents a group which can be replaced by an arylaminoresidue, and Z and Z represent a hydrogen, a halogen or a sulphonic group,

with aromatic amines containing at least one halogen atom in m-position to the amino group and preferably subjecting the compounds thus obtained to a sulphonating operation.

This process is in so far of great value for the important class of the alphylidoanthraquinone dyestuffs as the derivatives which contain in the alphylidorest a halogen atom in meta position to the imido nitrogen possess the unexpected property of giving much redder shades.

Thus for instance the sulphonic acid of l-amino-Q-methyll m chloranilidoanthraquinone dyes unmordanted wool violet shades, whereas the respective anilido-, ptoluido-, o-toluido-, m-toluido or p-chloranilidoderivatives give blue or violet-blue shades. The sulphonic acid of l-hydroxy-lm-chloranilidoanthraquinone yields red-violet tints, whereas the respective p-toluidoderivative dyes wool blue-violet shades.

The following examples illustrate the invention, the parts being by weight.

Example 1 10 parts of l-amino-2-methyl-4-bromanthraquinone, 40 parts of m-chloraniline, 4

parts of anhydrous potassium acetate and 0.1 part of copper sulphate are heated under good stirring at 160 C. until a test dissolved in benzene does no more show any change in the coloration. 0n addition of alcohol the thus produced dyestufl base is precipitated in form of fine crystal leaflets, which are soluble in benzene with a violet and in concentrated sulphuric acid with a red-violetcoloration. The purified base melts at 27 6 C. By sulphonating the base, an easily water soluble dyestuif is obtained, which dyes wool from an acid bath pure violet tints of an excellent fastness to light. This dyestuif is also very suitable for W001 printing. By introducing a second sulphonic group in the halogenated alphylido residue a much redder dyestufi is obtained.

Emample 2 10 parts of 1-amino-4-hydroxyanthraquinone, 20 parts of m-chloraniline, 60 parts of alcohol and 10 parts of hydrosulphite are heated under the reflux condenser in an indifferent atmosphere until the formation of the dyestufi base is finished. By sulphonating the base thus produced a dyestuil' is obtained which dyes wool violet-red tints.

Ezvample 3 Example 4 If the l-hydroxy-2-4-dibromanthraquinone used in the Example 3 is replaced by l-amino-Q-4-dibromanthraquinone, a dyestufi base is obtained which on sulphonation with oleum yields a dyestuif dyeing wool reddish blue shades.

E wample 5 10 parts of the dyestuff base obtained according to the Example 4 are heated with 20 parts by volume of a 38 per cent aqueous potassium sulphite solution and 40 parts of phenol until complete solubilization of the base has occurred. The phenol is then blown of by steam and the dyestufi is precipitated by salting out, filtered off and dried. The thus obtained dyestuff dyes wool violet-blue tints which do not change in the artificial light.

' E wample 6 23 parts of the potassium salt of l-amino- 2-4-dibrom-5-anthraquinonesulphonic acid are heated under the reflux condenser with 250 parts of water, 16 parts of m-chlor-aniline, 6 parts of sodium carbonate and 1, 5

the condensation is finished. On addition of acid to the reaction mass, the obtained condensation product is precipitated. By further treating same with potassium sulphite and phenol according to the Example 5, the bromine atom in the B-position is replaced by a sulphonic group yielding a dyestufl' which dyes wool very beautiful and fast reddishblue shades. Owing to its very good solubility it may successfully be used for W001 printing.

In the examples mentioned above the mchloraniline can be replaced by other m-halogen substituted aromatic amines. In gener- :11, if the aromatic amines which have been used up to now for the preparation of alphylidoanthraquinone sulphonic acids are replaced by their derivatives having at least one m-position to the amino-group substituted by a halogen atom. the dyestufi bases obtained yield after sulphonation very useful dyestuffs of a much redder shade.

The dyestuffs and their bases obtained according to the above described process posparts of crystallized copper sulphate, until sess the following reactions:

' Table I Solution in Dyestufi base 01 the formula In dry form Cone 2804 Alcohol Acetic acid Benzene V )a 13111: Beautiful leal- Violet-red Red-violet, Insoluble in cold Violet-blue Violet GH: lets flunescenoe alcohol Violet-blue in warm alcohol Prepared according to the Example l Dark violet Dull blue- Violet Violet-red in warm Violet-red Red-violet needles green alcohol FQ H Prepared according to the Example 2 OH 00 I B Very finetvlio- Green-brown Blue-violet Inslolulpl? in cold Violet-red Violet r c crys a s a co 0 Violet in warm alcohol HQ H Prepared according to the Example 3 Table I-Oontiiiued Solution in Dyestufi base of formula In dry form 0 Cone. H2804 zig wm Alcohol Acetic acld Benzene ITTH2 Little dark Dull blue Violet, red Insoluble in cold Violetblue Violet-blue Br blue crystals fluorescence alcohol Pale violet-blue in warm alcohol Prepared according to the Example 4 IIIH CO Veryfinedark Nearly color- Violet-grey Insoluble in cold Greenish blue Insoluble Br blue crystals less alcohol, violetblue in Warm alcohol YQ H Prepared according to the Example 6 Table I I Solution in Dyestufi In dry form Water m d er SO H2 under addi- Water addgllgn of S0 11, tion of boric acid Alcohol Prepared according to Ex- Dark bluepowder Violet Orange Violet Red-violet, red Violet am e1 fluorescence Prepared2 according to Ex- Darkbluepowder Violet-red Violet-rod Vlolet-blue Violet, red fiuo- Red-vlolet am e rescence Prepared according to Ex- Dark bluepowder Violet-blue Blue flocs Pale yellow-green Green-blue Blue am e Prepared according to Ex- Blue-grey powder Violet Dull reddish Dull violet Blue, red fluo- Violet am e rescence Preparled according to Ex- Violet-bluepowder Blue viglett precip- Pale blue-grey Blue-green Blue amp e 5 1 a e Prepared according to Ex- Dark-blue powder Blue Rose Greyish, after a Dull blue-green Blue ample 6 moment red What I claim is 2- 1. The dyestuffs of the anthraquinone seings of reddish-blue to red-violet shades. ries of the general formula:

i C O\ Z O O U C? coloration, yielding on animal fibres fast dyehalogen wherein X represents an arnino or hydroxy 2. The dyestufi of the anthraquinone series of the formula:

N Ha

I o 0 01 U OHS oo sour which is in dry state a dark blue powder, easily soluble in water with a violet coloration, soluble in concentrated sulphuric acid with a violet coloration, which becomes redviolet with a red fluorescence on addition of boric acid and which dyes unrnordanted wool pure violet tints of excellent fastness to light.

3. The d estufl of the anthraquinone se ries of the ormula:

GO GO SOa which is in dry state a dark violet powder, easily soluble in water with a red-violet coloration, becomin blue violet on addition of sodium hydroxi e, soluble in concentrated sul huric acid with a blue violet coloration, which becomes red-violet on addition of boric acidand which dyes unmordanted wool pure red-violet tints.

4. The dyestuff of the anthraquinone series of the formula:

sod! QUE which is in dry state a dark-blue-violet powder, soluble in hot water with a violet coloration, which becomes blue-green on addition of sodium hydroxide, soluble in concentrated sulphuric acid with a yellow-green coloration, which becomes greenish-blue on addition of boric acid and which dyes unmordanted wool blue-violet tints of excellent fastness to washing and acids.

In witness whereof I have hereunto signed my name this 25th day of J une 1930.

SAMUEL VON ALLMEN. 

